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By John K. Alley

Despite the extensive use of fluorphlogopite, investigators do not agree as to its exact melting temperature. Data on other fluormicas and on related fluorsilicate systems are largely nonexistent. A knowledge of the melting temperature is necessary for the effective synthesis and use of fluorphlogo¬pite or other fluormicas. The increasing use of two- and three-mica systems to yield polycrystalline ceramics has made more urgent the need for melting temperature information concerning these other fluormicas. This report is part of a program by the Bureau of Mines to synthesize large-size or large-crystal fluorphlogopite and develop a usable reconstituted fluormica sheet. The melting temperature of fluorphlogopite, K2Mg6A12Si6020F4, was found to be 1,383° ±2° C. This temperature was found by studying single crystals of fluorphlogopite, heating behavior of glass of fluorphlogopite composition, and the actual crystallization of fluorphlogopite from a melt that had been heated above 1,430° C. The formation of forsterite or norbergite was directly proportional to the loss of volatiles during the experimentation. Many trials revealed that the only reliable seal was a thick platinum sheet with welded seams. If no volatiles were lost, neither norbergite nor forsterite were formed; fluormica was then the only product. Excellently formed crystals of forsterite with an optical sign different from ordinary forsterite were obtained during the single crystal melting experiments. These crystals resulted from a slow loss of volatiles. A congruent melting of fluorphlogopite is indicated by the data of this report; however, incongruency within a small temperature range is not precluded. A more refined method using phase equilibria-quench methods would be necessary to settle the question absolutely.

Jan 1, 1962

By Clark F. Grain

These investigations were undertaken as part of the Bureau of Mines program for the development and evaluation of high temperature nonmetallic materials. This report consists of thermal expansion and phase inversion measurements by high-temperature X-ray diffractometry on the principal oxides of beryllium (BeO), calcium (CaO), titanium (TiO2 ), zirconium (ZrO2 ), hafnium (HfO2), and thorium (ThO2); all were high-purity commercially available oxides. Thermal expansion values were calculated from unit cell dimensions measured at selected temperatures. Expansion was determined parallel to each major crystallographic axis for the anisotropic oxides: BeO, TOi2, ZrC2, and HfO2. Combined random and systematic errors in the thermal expansion values are considered to be less than 3 percent of the total expansion at 500° C. and approximately 2 percent at 1,000° C. No hysteresis in the expansion curves was noted between heating and cooling cycles. The Bureau's values were compared with published expansion measurements obtained by X-ray diffraction, dilatometric, interferometric, and telemicroscopic techniques. For anisotropic oxides, average linear expansion values were calculated from the volume expansion.

Jan 1, 1962

By E. C. Perkins

As part of a program for developing methods of using domestic titanium deposits, the Bureau of Mines investigated methods for chlorinating titanium slags prepared from titaniferous minerals by electrosmelting. Titaniferous slags were made from ilmenites in the following deposits: Valley County, Idaho; Trail Ridge, Fla.; Aiken, S. C.; and Maclntyre, N. Y.; titaniferous magnetite from Iron Mountain, Wyo., were also evaluated. The tests were made in two chlorinators, a 4-inch and a 36-inch unit. Preliminary testing was done in a 40-millimeter bench-type unit. Chlorine gas was contacted with a loose mixture of titaniferous slag and carbon at a high temperature to form titanium tetrachloride. The moving-bed system used in this work involved a downward movement of feed countercurrent to the chlorine flow, and residues continuously removed from the bottom of the reactor. The performance characteristics of these slags depended on their composition, which varied widely according to the geographic source of the ore. The results showed that all but two of the slags could be chlorinated as effectively as rutile, converting 70 to 80 percent of the titanium to the tetra-, chloride. The two slags that proved difficult were made from New York ilmenite and Wyoming titaniferous magnetite. These slags contained enough magnesium to cause clinkering, which necessitated that the bed be prematurely withdrawn before more than 70 percent of it could react. The iron content of the slags did not interfere with operating the chlorinators. The data from the 4-inch and the 36-inch units were in agreement on the relative amenability of the slags to chlorination.

Jan 1, 1962

By M. L. Bowser

Pulse-forming circuitry is described for use in explosives research that requires precise synchronization and control of events in order to investigate detonation parameters. Included are pulse generators for oscilloscope sweep control, counterchronograph actuators, and a raster-type oscillographic method for the determination of velocities of detonation that are applicable to studies on solid, liquid, and gaseous detonations. INTRODUCTION Prom time to time, requests have been received for information on electronic circuitry used in explosives work at the Explosives Research Laboratory, Bruceton, Pa. The methods used are not entirely original;4 5 6 however, modifications of earlier techniques and some novel design aspects have resulted in time-tested methods that warrant a more detailed description.

Jan 1, 1962

By Bruce I. Thomas

Reconnaissance studies of beach sands along the eastern part of the Gulf of Alaska were conducted by the Bureau of Mines to determine if any of these coastal areas warranted investigations as possible sources of valuable minerals. Because of difficult access and limited transportation facilities only a minimum of sampling, surveying, and camping equipment is utilized to obtain spot samples from key areas as well as information indicating the location, size, and character of the deposits. Such data were obtained from beaches located along approximately 247 miles of the Gulf of Alaska coastline during parts of the 1957 and 1958 field seasons. A total of 201 3-inch-diameter auger holes, spaced roughly at 1 mile intervals, were bored by hand methods to depths ranging from 3 feet to 27 feet; also 33 shovel samples were collected from selected localities. Samples were reduced to a rough concentrate in the field by panning; the rough concentrates were shipped to the Bureau of Mines laboratory at Juneau for further concentration and for petrographic and chemical analyses. Particular attention was given to the heavy-mineral content of the concentrates, although the types and relative amounts of rock-forming minerals were also determined. The reconnaissance indicated that, generally, the valuable mineral content of the beach deposits was too low to be of further interest except in the vicinity of Yakutat and Lituya Bays where erratic but possibly significant concentrations of magnetite and/or ilmenite were found. At Yakutat, about 20 miles of beachline extending southeasterly from Ocean Cape, yielded samplas containing from 1 pound to over 300 pounds of iron and from a trace to over 100 pounds of titanium dioxide (TiO2) per cubic yard of beach material. However, the higher grade samples represented local concentrations of minor importance. The general tenor of the Yakutat beach, as indicated by the airthmetical average of 27 auger-hole samples, is about 35 pounds of iron and 20.5 pounds of titanium dioxide per cubic yard of beach material. Ilmenite is the predominant heavy mineral of the beach deposits in the vicinity of Lituya Bay, but it was found in concentrations only in limited areas near the

Jan 1, 1962

By H. R. Babitzke

The purpose of this investigation was to develop an alloy of columbium for use at high temperatures and for nuclear applications. The properties of possible alloys were determined, and the more promising ones were selected for further improvement. Criteria for selection were machinability, hardness, workability, tensile strength, and oxidation resistance. Thirteen 100-gram ingots, ranging from 100 percent columbium to 100 percent vanadium, were prepared and subjected to various tests. Also included for comparison were zirconium and the zirconium alloy, zircaloy-2. Test results showed that a columbium alloy, containing 10 atomic percent vanadium merits further development. Besides being workable at room temperature, the columbium-10 atomic percent vanadium alloy has oxidation resistance superior to the other alloys of the series and is also superior to zirconium or zircaloy-2. The latter two materials have comparable neutron-absorption cross sections. The strength and hardness values of the alloys tested were found to increase with increasing vanadium content, reaching a maximum at 50 atomic percent vanadium and decreasing with further increase in vanadium. This behavior is typical of binary alloys wherein each element will retain any proportion of the other in solid solution. INTRODUCTION There is an increasing need for alloys for service at high temperatures. Since current world reserves of columbium metal approximate 1,500,000 tons (1),4 this metal is now readily available. Columbium can ties; be considered a practical base material for high-temperature alloys required in nuclear reactors and in aircraft and space vehicles. General requirements chosen are: (1) Workability, (2) satisfactory mechanical properties at temperatures approaching 1,000° C., and (3) resistance to oxidation at such temperatures.

Jan 1, 1962

By R. W. Van Dolah

A premature detonation of an explosive charge occurred on January 30, 1961, at a face being prepared for blasting in the underground Jefferson Island Salt Mine, Diamond Crystal Salt Co., Jefferson Island, Iberia Parish, La. The accidental blast injured the powderman fatally; his helper was injured also, but recovered. The accident represents the first fatality reported to the Bureau of Mines in connection with the use of ammonium nitrate-fuel oil (AN-FO) blasting agents in underground mining in the United States. Representatives of the Bureau of Mines Explosives Research Laboratory, Pittsburgh, Pa., and field representatives of the Bureau's Health and Safety Activity conducted the investigation, upon request of the manufacturer of the ammonium nitrate being used and with concurrence by the mine management.

Jan 1, 1962

By J. B. Gayle

Commercial flotation plants operate on a continuous basis that is not simulated closely by the batch testing methods widely used in Bureau of Mines laboratory studies of flotation, Batch methods indicate whether a particular separation is possible but provide little or no information about the rates at which such separations can be effected in continuous operation, Therefore, laboratory equipment suitable for testing on a continuous basis was assembled for an investigation of a number of the operating variables that influence the flotation of coal. The results of these tests lead to the following conclusions: 1. Flotation recoveries were markedly influenced by variations in the percent solids in the feed, However, the relation between these variables is complex and depends on the particular coal and operating conditions used. Flotation rates generally increased with increased cell concentrations.

Jan 1, 1962

By R. P. Maloney

Since mining operations began in 1900, Government geologists and mining men have periodically recorded the presence of the minerals of mercury and antimony in the extensive gold placer deposits near Flat in the Iditarod district of the Yukon River region, Alaska. No serious effort was made to recover the cinnabar contained in the gold placer gravels, and there is no evidence that veins of cinnabar and stibnite exposed in the placer operations (as reported by the Geological Survey) were ever explored or developed. A large monzonitic intrusive, which is the dominant geologic feature of the immediate area, is believed to be the lode source of the valuable minerals in the placer deposits. In contact with the monzonite are argillite and quartzite, metamorphic products from the Cretaceous shales and sandstones.

Jan 1, 1962

By J. G. Donaldson

Nickel containing less than 0.01 percent of total metallic impurities was produced at the Rolla Metallurgy Research Center of the Bureau of Mines by electrodeposition from purified electrolytes. The first report on this research4 described purification of electrolytes by selective precipitation and by liquid-liquid extraction. This second report describes a procedure: or electrodepositing high-purity nickel from electrolytes purified by passing a nickel ammine solution through a column of an ion exchange resin. The nickel electroplated directly from the ammine solution without further treatment; a titanium cathode and two platinum anodes were used. The nickel deposit was dense, smooth, and adherent, and contained less than 0.001 percent each of cobalt, copper, and iron, and spectrographically detectable traces of aluminum, magnesium, and silicon. Nonmetallic impurities in the nickel metal were carbon and sulfur, each present in concentrations of less than 0.01 percent. The results of several experiments planned to purify solid nickel salts by zone refining are also reported. These salts, after purification, were intended for use in preparing electrolytes for deposition of high-purity nickel. Results were not encouraging so that the more promising ion exchange procedure was emphasized chiefly.

Jan 1, 1962

By A. A. Cochran

The purpose of this Bureau of Mines research was to investigate the theoretical and practical aspects of using ionizing radiation to promote chemical reactions that are of interest to metallurgists, and to carry out a radiation study of a suitable reaction. The effect of 44,000 roentgens per hour of 120,000-volt X-rays on the chlorination of highly pure mixtures of rutile, carbon, and various catalysts at temperatures up to 540° C. is described. At these low temperatures, recoveries were very low; however, in the eight different systems studied, an increase in yield due to X-rays was statistically significant in two instances and was of borderline significance in a third instance. In the other five systems, the differences in yield were not significant. Impurities and added catalysts caused relatively large variations in the yield of TiC14 from the reaction. Although the catalysts employed were reported in the literature as positive catalysts for the reaction, most of them were negative catalysts for the highly pure system studied. With only one exception, each increase in the purity of the charge resulted in a decreased yield of TiCl4. The experimental results indicate that many substances catalyze the reaction studied and suggest that the differences in reactivity of the charge stocks may be due to their various contents of positive and negative catalysts.

Jan 1, 1962

By R. Barany

In this paper, closed expressions have been obtained for the frequency spectrum of a Born-Karman square lattice in terms of elliptic and hyperelliptic integrals. This work is part of continuing research by the Bureau of Mines with the thermodynamic properties of metals and minerals. Although other workers have obtained various types of approximations for the general case of the frequency spectrum of a square lattice, no one previously has obtained closed analytic expressions for this spectrum. To understand the optical and thermodynamic properties of crystals, several investigators have studied the distribution of frequencies of normal modes of vibration of the crystal lattice. Born and Karman3 laid the foundation for the theory of lattice dynamics and obtained detailed results for the case of a one-dimensional lattice. Blackman4 used numerical techniques to estimate the frequency distribution of a two-dimensional square lattice. Mbntroll5 analytically determined the frequency distribution of a square lattice for a particular value of the force constants. He also studied the more general problem and obtained some analytic approximations, using the method of moments. However, the calculations by this method were so difficult that it was not always practicable to carry them out. Van Hove6 and Montroll7 studied the nature of the singularities in the frequency spectrum of both a two and

Jan 1, 1962

By R. L. Gall

This report describes Bureau of Mines experiments in gasifying coal in a helium-heated tube-coil reactor. The purpose of this work was to investigate helium as a medium for transferring heat from a nuclear reactor to gasify coal or for use as high-temperature process heat. A laboratory-scale system was designed and constructed to demonstrate feasibility. In preliminary tests with this system, in which the coal was fed as a water slurry, the helium-heating and recycling equipment operated well. Considerable difficulty was experienced, however, in preheating coal slurry to the desired range of 400° - 1,000° F. without plugging the preheaters. Five different preheaters plugged with coke or with salts leached from the coal. The longest operating period wan 12 hours. These difficulties were partly due to the relatively small equipment and flow rates. The gasifier processed l pound per hour of low-rank coal at 300 p.s.i.g. and 1,800° F., with the carbon conversion limited to 20 to 30 percent by the short residence time and slow heat-transfer rate.

Jan 1, 1962

By Frank A. Peters

This evaluation of the sulfurous acid process for the production of metallurgical-grade alumina is the first of a series concerning various known methods of extracting alumina from low-grade aluminous materials and was undertaken to permit comparison with other processes. In the process with which this Bureau of Mines report is concerned, calcined clay is leached under pressure with 20 percent sulfurous acid and then filtered to remove a siliceous residue. The aluminum sulfite remaining in the filtrate is precipitated as a monobasic sulfite which, together with iron sulfite, is then decomposed under pressure to form a crude alumina hydrate and iron oxide. This intermediate product is purified in a modified Bayer process to yield alumina suitable for electrolytic reduction to aluminum. A study estimate (16)3 is used for these evaluations. The capital cost, not including land, is estimated at $95,701,600 on a Marshall and Stevens index basis of 240.0 for a plant producing 1,000 tons a day of alumina or 350,000 tons a year. The annual operating cost for this size plant is estimated at $22,831,100 or $65.23 per ton of alumina using clay at $1 per ton. Depreciation and local taxes are included in the estimate, but profit and Federal taxes are not considered.

Jan 1, 1962

By J. R. Nettle

The development of a process for upgrading offgrade titanium metal by electrorefining in molten salt led to an investigation of the electrotransfer characteristics of selected metals when alloyed with the titanium to be refined. Previous tests on seven binary titanium alloys showed that the degree of transfer of the alloying constituent depends on the constituent and on the operating procedurese.5 This report describes tests on electrorefining ternary mixtures of titanium with selected metallic elements. Ten alloys were prepared from high purity titanium and 2-1/2 percent of each of the metal pairs selected from the same elements used in the binary study; manganese, vanadium, chromium, zirconium, tin, molybdenum, aluminum. Operating variables were similar to those investigated in the binary alloy study that gave minimum alloy metal transfer. The data presented indicate the transfer characteristics of the various metals and combinations tested relative to each other.

Jan 1, 1962

By Robert H. Merrill

Several investigators have obtained solutions for the concentration of stress around circular, ovaloidal, elliptical, and rectangular holes in an elastic, isotropic, semiinfinite plate subjected to uniaxial and biaxial stress. These solutions are used to evaluate the changes in stress around openings immediately under the undercut normally used in conventional block caving operations. The evaluations are based on the assumption that a horizontal undercut removes most of the vertical component of a biaxial stress field. The location and magnitude of the significant changes in stress concentration around the opening are computed. Conditions under which the assumptions used in the evaluations may or may not be consistent with conditions around block caving mines are discussed, and examples of preferred opening shapes for a biaxial (hydrostatic) stress field are shown. This report is a summary of one phase of an investigation to establish design methods for the size and shape of mine openings used in block caving mining methods .

Jan 1, 1962

By W. T. Abel

The rate of the steam-carbon reaction, which is of fundamental importance to coal gasification, was determined by passing steam over graphite specimens suspended in an electrically heated tube. The measurements were made at 1,900° to 2,400° F. and at steam-feed rates of 0.1 to 2.0 moles of steam per mole of carbon per minute. At the maximum steam-feed rate, the reaction rate of carbon ranged from 0.4 percent per minute at 1,900° F. to 7 percent per minute at 2,400° F. Up to about 2,200° F., the steam-feed rate had only a slight effect; above this temperature, it limited the reaction velocity when the final mole fraction of steam in the reaction products was much less than 1.

Jan 1, 1962

By W. A. Calhoun

This report gives results of metallurgical investigations performed by the Bureau of Mines on mineral samples taken during April 1959, from Hawaiian bauxite deposits on the islands of Kauai, Maui, and Hawaii. The bauxite samples were tested at the Bureau's Rolla Metallurgy Research Center, Rolla, Mo., to determine if alumina could be extracted. The results were encouraging. Extraction of the alumina by the American Bayer type digest of crude ore samples from Kauai, Maui, and Hawaii recovered 78.8, 73.1, and 70.0 percent, of the total alumina, respectively. These recoveries were increased to 82.8, 85.5, and 79.5 percent by modifying the treatment, which consisted essentially of calcination and weak caustic desilication to provide a residue. The residue was then treated with calcium oxide and digested in a strong caustic solution to extract the alumina.

Jan 1, 1962

By J. V. Batty

Radioisotopes of selenium (se78) and tellurium (Te123) were successfully employed by the Bureau of Mines as tracers in metallurgical research directed to developing improved methods for volatilizing these elements from low-tenor raw materials. Prior research, guided and controlled by conventional analytical methods, was seriously hampered by inconsistent selenium and tellurium analyses, by the slowness of the conventional chemical methods, and by the poor accountability of these volatile elements in test products. Methods were devised and evaluated for admixing the radioactive tracer with typical raw materials and then following the deportment of the selenium and tellurium by radiometric methods with occasional chemical analysis checks. These techniques were found unusually effective in (1) quantifying the completeness and the rate of volatilization of selenium and tellurium while heating the raw materials at different rates to different temperatures and (2) accurately tracing and quantifying the distribution of minute amounts of these volatile elements in the several products made by high-temperature treatment and in the several units comprising the experimental equipment.

Jan 1, 1962

By J. G. Haymes

This report by the Bureau of Mines is the first of two proposed papers on evaluation of spectrophotometric, spectrographic, polarographic, and other analytical methods for quantitatively determining impurities in high-purity tungsten. Some of the methods described are standard methods that have been successfully applied to determine low-level impurities, several are modifications of known methods, and some procedures are entirely original. The Bureau of Mines is actively engaged in tungsten research because tungsten has an extremely high melting point, in fact the highest of any known metal. The metallurgist must know the content of impurities in tungsten because of the marked effects even micro amounts of impurity elements have on its physical properties. The Bureau procured a number of analyzed samples of above-average purity from research laboratories of companies engaged in production and fabrication of tungsten. These samples were investigated by the analytical procedures of those companies for several metallic impurities. Subsequent analytical laboratory determination of impurities in these samples agreed with the analyses as reported. With this assurance that analytical methods were basically accurate for metallic impurities, procedures for the determination of several of these elements were modified to lower the limits of detection and increase the sensitivity of methods. Carbon and the gases hydrogen, nitrogen, and oxygen were determined by standard instrumental methods, modified to provide greater sensitivity for reliable determinations when content of these elements was low. After the reliability of the modified procedures was affirmed, they were used as a product evaluation guide in the development of a vapor-plating technique for the production of high-purity tungsten. The following list of elements can be determined by one or more of these methods: AI, B, Be, Ca, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, S1, Sn, Ti, V, and Zn. In addition, a vacuum-fusion method for the determination of H, N, and 0, and a conductometric method for carbon are described. Lower limits of determination and detection for each element listed are given.

Jan 1, 1962